Mixtures of cationic and non-ionic surfactants, chlorinated triphenylmethanes and tanning agents and union dyeing therewith



April 20, 1965 H. E. MILLSON ETAL 3,179,483

MIXTURES OF CATIONIC AND NON-IONIC SURFACTANTS, CHLORINATED TRIPHENYLMETHANES AND TANNING AGENTS AND UNION DYEING THEREWITH Filed Feb. 14, 19 62 5 Sheets-Sheet 1 500 600 700 WA VEZ'A/GTH M/u/M/c'kwls ICIE 1 WA VEaFA GH/ M/Z L lM/CFOMS m 20, 1965 H. s. MILLSON ETAL ,179

MIXTURES OF CATIONIC AND NON-IONIC SURFACTANTS, CHLORINATED TRIPHENYLMETHANES AND TANNING AGENTS AND UNION DYEING THEREWITH Filed Feb. 14, 1962 s Sheets-Sheet 2 676 6' C TANC 6' 400 500 600 700 W4 V'ZF/VGTH M/lL/M/C'IO/VS J IEZ 5 WA V61 6W6 7H MI! 1 lM/CZOA/S I IL; 4

Apnl 20, 1965 H. E. MILLSON arm. 3, 79,

MIXTURES OF CATIONIC AND NON-IONIC SURFACTANTS, CHLORINATED TRIPHENYLMETHANES AND TANNING AGENTS AND UNION DYEING THEREWITH 5 Sheets-Sheet 3 Filed Feb. 14, 1962 INVENTORS HEMY 6. 144M450 604462 .7. 61/1656? JAM'S OAMMMZ'I 500 00 WA V'llF/VGTH Mil L/M/CKONS v WA V5! 6176 7/! MI! L IMICROIVS 2 m wmo WMETNUW NRWN April 20, 1965 Filed Feb. 14, 1962 H. E. MIXTURES OF CATIONIC AND TRIPHENYLMETHANES 5 Sheets-Sheet 4 .55 .50 I f; as

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P" 2 1965 H. E. MILLSON ETAL 7 MIXTURES OF CATIONIC AND NON-IONIC SURFACTANTS, CHLORINATED TRIPHENYLMETHANES AND TANNING AGENTS AND UNION DYEING THEREWITH Filed Feb. 14, 1962 5 Sheets-Sheet 5 WA VEM-WGTH M/U/M/CEO/l/S INVHVTORB H'A/KY 5. M/(LSOA/ 11m? J. sues JAMES DAMM/C'Cl g United States Patent M MIXTURES OF CATIONIC AND NON-IONIC SUR- FACTANTS, CHLORINATED TRIPHENYLMETH- ANES AND TANNING AGENTS AND UNTON DYEING THEREWITH Henry E. Millson, Plainfield, Elmer J. Glaeser, Middlesex, and James Dammicci, Raritan, N.J., assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine Filed Feb. 14, 1962, Ser. No. 173,238 Claims. (Cl. 8-21) The present invention relates to a novel process for leveldyeing mixtures of nitrogenous materials with presentlyavailable dyes which previously could not be so utilized. More particularly, it is concerned with a process for leveldyeing unions of natural and synthetic nitrogenous fibrous materials, especially wool and nylon unions.

Still more specifically, the invention also presents novel dyeing assistants which enable the mixed nitrogen-containing materials to be colored with the desired dyestuffs and which at the desired pH range cause more nearly an equal strike of such dyes on both types of fiber in the union. Resultant dyeings are characterized by excellent strong, level, shades. They exhibit no physical damage to the material.

As used in this discussion, the term level-dyeing means so-dyeing such a union as to produce a shade of approximately equal depth or strength on both the natural and the synthetic nitrogenous fibers. In general, the present invention may be used for level-dyeing mixed nitro genous materials in various physical forms. However, its most comonly-encountered applications are in the dyeing of yarns and fabrics which comprise mixtures of synthetic and natural nitrogenous fibers. Therefore, these mixed yarns and fabrics will be taken as illustrative. Herein, for purposes of simplifying their identification, they will be referred to as unions.

As contemplated by the present invention, the term nitrogenous fibers includes both natural and synthetic materials, most of the latter being organic, hydrophobic materials. These nitrogenous fibers may be classified generally into two broad groups as (A) proteins and as (B) synthetics. As used in this discussion, group (A) includes both ntaural and synthetic proteins, and group (B) ineludes various types of synthetic, organic, nitrogen-com taining, polymeric fibers,

The older group, group (A), often is more precisely defined as a basic, nitrogen containing group, i.e., as materials wherein the nitrogen is present in a basic form. This class includes such natural protein fibers such as wool, mohair, fur, hair, alpaca, real silk, Tussah silk and the like. It also includes synthetic protein fibers such as those derived from corn, peanuts, milk and the like. The present invention is primarily concerned with the natural fibers of group (A). In practice, wool will probably be the most frequently encountered type. Therefore, it will be taken as illustrative in this discussion.

In recent years, industry has developed a large number of varied synthetic fibers, each having desirable properties. Some of these comprise the above-noted group (B) of this invention. Among these are included various superpolyamides, known generally in the trade as nylons. These nylons are of primary interest in the present invention as being the synthetic fibers most commonly encountered in the problem unions .to be dyed. Accordingly, they also will be taken as illustrative herein.

Therefore, for purposes of this discussion wool-nylon unions are used as illustrative. They will be more frequently encountered in actual practice than will other blends and because they present all the typical problems. In general, however, features discussed with respect there- 3,179,483 Patented Apr. 20, 1965 to are also applicable to the other natural and synthetic fibers of group (A) and other synthetic fibers of group (B).

Despite the varied, but advantageous, properties of these unions of natural and synthetic fibers, in the past there has been available no satisfactory process by which they can be level-dyed with some types of conventional dyes at a pH in the range of from about 4.5 to about 6.5. This problem has proved particularly troublesome with respect to the illustrative wool-nylon unions.

In the past, attempts have been made to color woolnylon unions with a variety of dyes including acid dyes, milling dyes, acid-dyeing premetalized dyes, and the like. Acid dyes, including milling dyes, have better than average brightness but are lacking in fastness properties. Usually they are considered commercially unacceptable Where fastness properties are required, as in blends for suitings to be subjected to extended outdoor exposure. Acid-dyeing, premetalized dyes have the desired brightness and fastness properties but due to the low pH at which these dyes are applied, during the dyeing operation they cause tendering of the union material, especially wool. Consequently, coloring of wool-nylon unions has been largely restricted to the use of commercially-available neutral-dyeing premetalized dyes.

In a typical current process for applying such colorants, a dyebath is prepared by adding the required amount of Water to the dye vessel; adding about 0.25-4.0 weight percent of the neutral-dyeing, premetalized dye which has been prewet in a small volume of Water; and finally adding an ammonium salt, such as ammonium acetate, usually in amount of about three Weight percent on the weight of the fiber (owf.) to be dyed. Usually the dye bath is at about ambient room temperature and has a pH of about six. After the union material isentered into the dye bath, heat is applied and the union material is turned during the process to improve the levelness of the dyeing. Heating is continued to bring the dye bath slowly to the boil where it is maintained for a short time. Usually a second addition of amomniurn acetate (3% owf.) is then made and dyeing at the boil is continued until completed. The dyed material is then separated from the dye bath. rinsed and dried.

This procedure has several disadvantages. In the first place, the dye tends to strike or be absorbed by the nylon at a temperature between about l40-l60 F. Once the dye has struck, it tends to remain fixed. As a result, the shade of the dyed nylon is too heavy. With many dyes, attachment of the dye to the nylon fiber is uneven, resulting in a skittery or heathery effect which renders the dyed material useless for merchandising. In the second place, the dye does not strike the Wool until a higher temperature, i.e., on the order of some l70l90 F., is reached. By this time, much of the dye has been deposited from the dye bath on the faster-dyeing nylon. As a result, the Wool is only lightly, or weakly, colored, further aggravating the heathery or skittery effect.

Unfortunately, because of the temperature difference of the strike of these two materials, it has not been possible to obtain completely satisfactory union dyeings on these materials when neutral-dyeing premetalizeddyes are used. This has been especially difficult when the wool portion of the union has been carbonized (treated with sulphuric and then subjected to heating) to remove vegetable material as it is very difiicult to maintain a pH in the dye bath as high as about 5.5 to 6.0 due to the presence of residual sulphuric acid in the carbonized Wool. Should the pH become lower, i.e., more acid, the strike of the dye for the nylon may be altered or the wool may be tendered.

One method suggested to overcome this unevenness of strike is by the addition of a soluble chlorinated triphenylmethane to the dye bath in an attempt to hold oil the dye from the nylon during the early part of the heating period. This should permit the held-01f dye to be absorbed by the wool during the latter stages of the heating process. A soluble chlorinated triphenyl-methane does hold off the dye from the nylon. However, for some reason which we cannot presently explain, satisfactory increase in absorption of the dye by the wool does not occur. Consequently, this unabsorbed dye remains in the dye bath, is wasted, and adds to the expense of the operation.

Despite the advantageous properties of these woolnylon unions such as their increased strength, their lightness in weight, their greater wearing qualities, their resistance to shrinking and their greatly-improved resistance to wrinkling, prior to this invention, there still remained a need for a dyeing process for wool-nylon unions which would include the following desirable combination of features:

(a) Uniform strike on both wool and nylon;

(b) Level shades;

(c) Good penetration of the fiber by the dye;

(d) Maximum fastness properties of the dyed material;

and

(e) Good exhaustion of the dye from the bath thereby reducing needless waste with accompanying expense 7 in the operation.

Such a process should be easily and simply applied; it should enable satisfactory, level-dyeing to the desired deep shades using conventional neutral-dyeing premetalized dyes and it should avoid physical damage to the fibers, Most important, it should eliminate the skittery or heathery effect produced by the present conventional processes.

Surprisingly, in view of the need for such a dyeing process, and the previous lack of success in finding one, according to this invention such a procedure has been found.

In general terms, this new dyeing process may be simply described. The wool-nylon unions in the form of yarns, fabrics, non-woven webbing, etc., are

(1) Wet-out with water;

(2) Entered into a dye bath at ambient room temperature;

(3) The bath having the following general composition (a) The neutral-dyeing premetallized dye,

(b) A colloidized cationic surfactant,

() A non-ionic surfactant, and optionally,

(d) An anionic surfactant, 7

(e) At least one material of the group of tannic,

acid, gallic acid, quebracho and inorganic zirconium salts,

(1) A soluble chlorinated triphenylmethane,

(g) An ammonium salt, ammonia or acetic acid in amount sufiicient to produce a pH not lower than about 4.5, preferably 5.5-6.5;

(4) Heating the aqueous bath containing the union mater-ial slowly with stirring, or turning, to about 195 F. to 215 F. to transfer'the neutral-dyeing premetallized dye to the union material; and

(5) Separating the colored material from the aqueous bath; and thereafter conventionally rinsing and drying the dyed material.

A particular feature of the invention, as will be more fully discussed below, is the inclusion of the item (e) in the dye bath. Because the group includes tannic acid, for purposes of identification below these materials will be referred to as the tannic agent. However, tanning, as in processing hides into leather, is not involved in the present invention.

An advantage of our invention is that the order of addi- :1 tion of the components of the dye bath is quite flexible. Thus, in commercial dyeing, a union material may be entered into suitable dyeing equipment containing water only. Turning is started and the components of the dye bath the are entered as follows:

(a) The colloidized cationic surfactant,

(b) The nonionic surfactant,

(0) The anionic surfactant (optional),

(d) The tanning agent,

(2) The pH controlling agent,

(f) The soluble chlorinated triphenylmethane, (g) The dye.

It is a further advantage of our invention that the surfactants, the tanning agent and the soluble chlorinated triphenylmethane may be combined, as by prernixing in certain definite proportions, to form a composition which may be introduced into the dye bath in a single step. Compositions of this type come within the scope of our invention and will be discussed more fully below.

THE DYESTUF F S UTILIZED the older acid-dyeing type which dye levelly at a pH of about four to six. The latter contain sulfonic acid groups or alkali-metal salts thereof. In the neutraldyeing type with which this invention is concerned, the sulfonic groupings have been converted to some modified grouping such, for example, "as the sulfonamides. This change in the molecular structure also modifies the dyeing characteristics. Unlike the acid-dyeing type, they will not dye levelly at the usual acid-dyeing pH range of about four to six. For optimum results, it is usually necessary that this type be dyed from a bath having a pH of about six to eight. It is an advantage of the present invention that this is not a limitation on using these dyes therein.

In general, neutral-dyeing premetallized dyes as discussed herein may be considered to be partial metal complexes of azo compounds formed from one atom of a trivalent metal such as chromium or cobalt complexed with two molecules of the azo compound. For illustrative purposes, a composition of a number of commercially important neutral-dyeing, premetallized dyes follow.

Red 1: The cobalt complex of one atom of cobalt chelated with two moles of the dye obtained by coupling diazotized ortho amino phenol 4 sulfonamide with beta-naphthol. I

Red 2: The chromium complex of one atom of chromium and two moles of the dye obtained by coupling diazotized ortho-amino phenol-S-sulfonamide with diphenylpyrazolone.

7 Yellow 1: The cobalt complex of one atom of cobalt and two moles of the dye obtained by coupling diazotized ortho-amino phenol-4-sulfo namide with acetoacetanilide.

Yellow 2: The cobalt complex of one atom of cobalt and two moles of the dye obtained by coupling diazotized ortho-amino phenol-l-sulfonamide with phenylmethylv pyrazolone. 7

Orange 1: The cobalt complex of one atom of cobalt and two moles of the dye obtained by coupling diazotized ortho-amino phenol-4-sulfonamide with benz'oaceto nitrile. Orange 2: The chromium complex of one atom of chromium and two moles of the dye obtained by coupling diazotized ortho-aminophenol-4-sulfonamide with (4 chloro-phenyl) -methylpyrazol one.

Violet 1: The cobalt complex of one atom of cobalt and two moles of the dye obtained by coupling diazotized ortho-amino phenol-S-sulfonamide with beta-naphthol.

Brown 1: The chromium complex of one atom of chromium and two moles of the dye obtained by coupling ortho-amino phenol-4-sulfonamide with benzoylacetonitrile (see US. Patent 2,366,633).

Scarlet 1: The chromium complex of one atom of chromium and two moles of the dye obtained by coupling diazotized ortho-amino phenol-4-sulfonamide with diphenylpyrazolone.

Blue 1: The chromium complex of one atom of chromium and two moles of the dye obtained by coupling diazotized 1-amino-2-hydroxy-4-sulfonamide with 5,8- dichloro-l-naphthol (or the half chromium complex of 2 (2 hydroxy 4 sulfonamidephenylazo) 5,8- dichloro 1 naphthol).

The indicated dye names are those of the new Color Index. Other illustrative dyes of this type are disclosed in US. Patent No. 2,775 ,581.

The amount of dye, or dyes, added to the dye bath will depend upon (a) the depth of shade demanded by the customer and (b) the number of dyes required to match that shade. Commercial dyeings may require from about 0.25 to 3 weight percent (owf.). In the development of the invention, a good practice was found to be the use of about one percent of dye (owf.).

USE OF THE TANNIC AGENT A particular feature is the use of the tannic agent, i.e., the tannic acid or its equivalent. It should be of good grade, containing a minimum of insoluble material which might combine With the dye to form an insoluble scum. It is highly unexpected to find that this agent not only increases'the strike of the dye for the wool, but also reduces the strike for the nylon. The strength. of the shade of the wool in a wool-nylon union dyed from the baths of this invention containinga tannic agent is about 40% or more stronger than an otherwise identical dyeing made without using the tannic agent. At the same time, the presence of the tannic acid reduces the strike on the nylon in this wool-nylon union by about 20%.

Amounts ranging from about 1.5 to 5 Weight percent (owf.) may be used but about two to three weight percent (owf.) will be found generally to comprise a good practice. In the presence of the tanning agent, wool appears to be capable of absorbing the held-off dye. The dye bath is substantially free from unabsorbed dye when the dyeing cycle is completed. This adds to the efficiency of the operation by avoiding the waste due to unabsorbed dye which, as noted above occurs when a soluble chlorinated triphenylmethane is used alone.

As to the amount of this agent to be added, it will be found to vary from about 1 to 5% (owf.). About 1 to 3 Weight percent will be found to constitute a good general practice.

In using the tanning agent, especially when using a zirconium salt, a minor portion of a soluble, chlorinated triphenylmethane may be added. This agent acts as an aid to the tanning agent. Eulan CN, a commercially-available pentachloro-dihydroxy-triphenylmethane sodium sulfonate sold by General Dyestutf Company of New York, is a good illustrative example of such materials. Commercially-available products may contain about up tosome 12% inert material. This factor should be allowed for in weighing the amount to be used.

USE OF THE SURFACTANTS In addition to strength or depth of shade, an important characteristic of a commercially-acceptable, dyed wool-nylon union is" a solid, level shade. As the rapidity of the strike on the wool is increased by the presence of the tanning agent, the dye appears to remain fixed. The dye is unable to dye otf-and-on which is a useful feature in obtaining level dyeinga We have found, however, that our combination of the cationic, nonionic and anionic types of surfactants is useful in promoting a leveling action in the application of these neutral-dyeing premetallized dyes. l

The novel process and compositions of this invention must utilize at least one cationic and one nonionic surfactant. Except when the tannic agent is: a zirconium salt there must be also at least one anionic surfactant. All of the surfactants which are employed are of known types. In each case, a number of such surface-active agents are readily available under a variety of commercial designations. Many examples of each type are shown in Detergents and Emulsifiers--up to date, published annually by John W. McCutcheon, Inc., of New York City. It is their combination and the method of combining them with the tannic agent which is responsible for unexpected success of this invention.

Illustrative of suitable cationic agents for use in the present invention are long-chain polyethylene, polyoxyethylene or ethylene oxides such as the condensation products of octadecylguanidine carbonate and ethylene oxide of US. Patent No. 2,574,510. Many products of this type are soft, wax-like and inconvenient to handle.

We prefer to use solid colloidized products such as those of U8. Patent No. 2,434,178; especially a colloidized product of octadecylguanidine bicarbonate and ethylene oxide (one mole to six moles, respectively) and which contains about 20% cationic surfactant. In general, useful results are obtained when about 0.5 to 5 weight percent (owf.) of the solid is used. About 1 to 2 weight percent (owf.) will be found to be good average practice. The use of the term colloidized cationic .sufactant in the specification and claims is limited to such products which are colloidized with hydrophilic colloids.

0f the various available nonionic types, one suitable type is frequently referred to as the phenolic type. These are commercially-available products obtained by condensing about one mol of an alkyl phenol with from about six to about ten mols of ethylene oxide. The alkyl moiety of the phenol should be a medium length chain of about six to ten carbon atoms. A typical illustrative product is that obtained by condensing one mol of nonyl phenol with nine mols of ethylene oxide. Other illustrative products include alkylaryl polyether alcohols such as Deceresol NI, sold by the American Cyanamid Company; and polyoxyethylene ether alcohols such as Renex 30; and urea-complexed polyoxyethylene ether alcohols such as Renex 35, both soldby Altas Powder Company; In general, amounts ranging from about 0.25 to 2.5 weight percenttowf.) are useful although 0.25 to 0.5 weight percent is a good practice.

In the cases of some neutral-dyeing premetallized dyes, addition of a small quantity of an anionic surfactant also will be found helpful. Illustratively, sulfonated naphthalene types are found useful. Such a surfactant is a mixed amyl-naphthalene sodium sulfonate, the mixture containing mono-, di, and triamyl groups. Amounts ranging from about 0.25 to 2.5 weight percent (owf.) are useful although about 0.25 to 0.5 weight percent (owf.) is a good practice. When zirconium sulfate or other zirconium salt is used in place of the tannic acid, or equivalent, the anionic surfactant may be omitted from the composition without detracting from the solidity of the shade. y A further advantage of our process is that the tannic acid, soluble chlorinated triphenylmethane and the surfactants also may be precombined in the required proportions, thereby reducing the labor and probability of error on the part of thedyer. Compositions of this type save res also constitute anembodiment of our invention. A typical illustrative composition of this type contains, by weight,

12.5 parts. of a colloidized surfactant of U.S. Patent No.

6.25 parts of the nonionic surfactant,

6.25 parts of the anionic surfactant,

37.50 parts of the tannic acid, and

37.50 parts of the soluble chlorinated t-riphenylmethane.

When eight parts of this composition is dissolved in 92 parts Water, five parts of the resulting aqueous solution will contain, based on the Weight of five parts of the material to be dyed,

1.0% colloidized cationic surfactant,

0.5% nonionic surfactant,

0.5% anionic surfactant,

3.0% tannic acid,

3.0% soluble chlorinated triphenylmethane.

Use of this composition causes excellent results to be obtained.

When a zirconium salt, such as zirconium sulfate or other equivalent salt as known in the industry, the specific salt not being critical here, is used rather than the tannic acid, gallic acid or quebracho; the anionic surfactant may be omitted. The following mixture is illustrative of those found useful in such cases:

33 parts of a colloidized cationic surfactant of US. Patent 46 parts of a soluble chlorinated triphenylmethaane,

17 parts of the zirconium salt, and

4 parts of the nonionic surfactant such as Renex 30 or Renex 35.

When one part of such a composition is dissolved in 99 parts water, five parts of the resultant solution contains 50 milliparts of the above composition, equivalent to one weight percent on five parts of material to be dyed.

Neutral-dyeing premetallized dyes are best applied from starting baths having a pH not lower than 4.5 and preferably about 5.0 to 6.5. To obtain this result, use of about three Weight percent (owf.) of an ammonium salt such as ammonium acetate, ammonium sulfate, ammonium chloride and the like, is a good practice. For those dyers who prefer to use acetic acid, the amount should be that required to adjust the pH to about 5.0-6.0. If the wool in the wool-nylon union has been carbonized, it will be necessary in most cases to neutralize the excess acid with ammonia to produce a dye bath having an acceptable starting pH of about 4.5 to 6.0.

The invention will be more fully described in conjunction with the following examples and drawings. Unless otherwise noted, all parts and percentages are by weight, concentration percentages of the ingredients in the dye baths are percentages based on the weight of the fiber and are indicated (owf.). Temperatures are in degrees Fahrenheit.

In conjunction therewith, in the accompanying drawings, FIGURES 1-10 are pairs of curves as drawn by a recording spectrophotometer showing dyeing strengths obtained on wool-nylon unions, both without and with the presence of the novel dye-bath compositions, W and N denoting without and W and N denoting with, respectively. Dyeing strength or color reflectance value may be defined as the reflectance of a dyed swatch at a certain wavelength as determined by means of the recording spectrophotometer. In the present work the spectrophotometer used was one of the type sold by the General Electric Company. The difference in strength between the two swatches is derived from the reflectance values by using the well-known Kubelka and Munk formula.

Unless otherwise noted, the test fabrics dyed were unions of wool and nylon 66 (spun). The test procedure used in the following example, Example 1, is illustrative of the'procedure presently employed in the textile industry for dyeing wool-nylon unions with neutral-dyeing, premetallized dyes.

Example 1 250 ml. water is added to a 600 ml. beaker and 50 mg. (1% on weight of fiber, hereinafter referred to as owf.) of the dye (Scarlet 1) is added. When the dye is thoroughly wet, 150mg. ammonium acetate (3% owf.) is

second 150 mg. of ammonium acetate is then added and boiling and turning continued for about 30 more minutes. The pH is about 5.8. Dyed pieces are then removed from the dye bath, rinsed and dried. The nylon is heavily dyed and the wool only lightly dyed.

The color value of the dyed pieces is then determined from color-reflectance curves obtained by means of a recording spectrophotometer, resultant curves being shown, in FIGURE 1, W (wool) and N (nylon). Using the color value of the nylon as a standard, or control, the color value of the wool is only 19%, indicating a poor strike of the dye for the wool.

For comparison, the following example illustratcsthe effectiveness of a novel equalizing composition of this invention in the application of the same neutral-dyeing premetallized dye of Example 1, to, the same Wool-nylon union. In this and the following examples, the nylon dye strength obtained by the procedure of Example 1 is taken as the standard, i.e., as being 100%.

i Example A dye bath is prepared as followsz Two 2.5 gram portions of the same fabric used in Example 1 are wet out, entered into the dye bath, raised slowly to the boil in about half an hour with turning, and dyed at the boil for one hour. The pH is about 4.8. The dyed fabrics are then rinsed and dried.

Color reflectance curves of the dyed pieces are also shown in FIGURE 1, being marked W (wool) and N (nylon). It will be observed that the strike of the dye for the wool has been greatly increased and that the color values of the two fabrics dyed in the presence of the equalizing additives are substantially equivalent, the difference of about three percent being undetectable by the average human eye. i

Repeating the experiment with the surfactants, the tannic acid and the chlorinated triphenylmethane added to the bath singly; both as solids andalso dissolved singly in portions of the dye-bath water; and after being physically premixed before dissolving in the dye bath all pro- Example 3 The procedures of Examples 1 and 2 are repeated, substituting the dye Orange 2 for the dye Scarlet 1. Spectrophotometric curves of the dyeings areshown in FIGURE 2. Numerical values of the strength of these dyeings as" obtained from these curves are N=l%; W=%; N=44%; and W'=50%. It will be observed that although the nylon W218 about six times as strong as the wool when dyed by conventional means, the use of the equalizing additives has caused the dye to strike the wool more rapidly and the strength of the dyed wool has been increased more than three times, the dyed wool being very slightly stronger than the dyed nylon. The dilierence is small and the dyeing is acceptable, being markedly better than could be previously obtained by the illustrative prior procedure of Example 1.

Example 4 The procedures of Examples 1 and 2 are repeated using the dye Yellow 2 instead of the Scarlet 1. spectropho tometric curves of dyeings made by these procedures are shown in FIGURE 3, the numerical values taken from these curves being 'N =100% (standard), W=10%, N=48% and W=53%. It will be observed from these data that the color strength of the nylon dyed by the conventional procedure practiced in the industry is about 10 times as strong as the wool, whereas wool-nylon unions dyed by the process of our invention difier only by about five percent, a difference barely perceptible to the human eye. The union dyeing is acceptable.

Example 5 The procedures of Examples 1 and 2 are repeated except the dye Blue 1 is used instead of the dye Scarlet 1. Spectrophotometric curves of the dyeings are shown in FIGURE 4. Color values measured from these curves are N=l00% (standard), W=50%, N=70% and W =68%. This difference of two percent between N and W is not perceptible to the human eye and the strength of these two dyed pieces would be considered to be identical. 1

a Example 6 The procedures of Examples 1 and 2 are repeated using the dye Red 2 instead of the Scarlet 1. Spectrophotometric curves of these dyeings are shown in FIGURE 5 from which the following numerical values are obtained:

spectrophotometric curves of the dyed pieces numerical values were obtained and are listed below:

Color Values in Percent of Dyed i 1 Pieces as Read from the Spec- Sarnple Designation Color (0.1.) trophotometrlc Curves (Reflectance Readings).

N W N W Yellow 1- 100 11 31 61 Brown 1- 100 17 44 65 Red 1 100 12 58 38 Orange 1 -1 100 13 43 58 It will beobserved that in every instance W (column 4) has a very poor colorvalue compared with N (column 3) indicating that the old and conventional method of applying neutral-dyeing premetallized dyes causes a verypoor strike of the dye on the wool.

' The color values of N (column 5) and W (column 6) indicate that when color is applied using our novel dye ing composition (Example 2) the dyed wool and nylon have more nearly approached the same strength due to a markedly increased strike of the dye on the wool When this occurs, there is less dye remaining in the dye bath for the nylon and consequently its strength is somewhat reduced. i

It will also be noted that in some instances the value for W is greater than the value for N indicating that this particular dye responds to the equalizing additives more readily. Thus, for samples D and E, nylon is dyed by the present conventional method about eight times as heavily as is the wool. In the presence of the equalizing additives, however, the wool is dyed heavier than the nylon (sample B) but the reverse is true for sample D.

Many dyes of this class, particularly the difiicult-to-dye colors such as Red 1, cause the above-discussed uneven dyeing or skittery effect to be obtained. Dyed fabrics are commercially unacceptable when the dye is applied by the presently-conventional methoddescribedl in Example 1. This skittery efiect is eliminated by our novel composition and process, the resultant dyeings are level and, uniform and the dyed fabrics are commercially satisfacw tory.

Example 8 The procedures of Examples 1 and 2 are repeated using, however, a 100-mg. mixture of the following dyes:

60 mg. of the dye Red 1 35 mg. of the dye Orange 2 5 mg. of the dye Blue 1 The strengths of the dyed pieces as determined from the spectrophotometric curves follow:

These results indicate that the novel dyeing compositions of this invention are useful in applying combinations of dyesto give a particular shade when dyeing wool and nylon unions. 7

Example 9 Dyeings are made as in Examples 1 and 2 except the dye Red 1 is used instead of the dye Scarlet 1, all the ingredients are multiplied 24 times, and dyeings are carried out in a reel-type machine. Spectrophotometric curves of the reflectances of the dye pieces are shown in FIGURE 6. Numerical values obtained from these curves follow:

N: 100% (standard) W=14% Example 10 Varioussamples of union-combinations of wool and nylon are dyed by the proceduresof Examples 1 and 2 except the dye Red 1, a difiicult-to-dye color, is used. The fabric combinations follow: 3

Wool-filament nylon as parachute cloth Wool-filamentnylon as tricot fabric Wool-filament nylon as taffeta fabric Wool-nylon 6 75% wool-25 spun nylon wool-15% spun nylon In each instance the strike of the dyefor the wool is increased by the use of the equalizing additives, levelness of the dyeings is improved and skittery effects are eliminated.

Example 11 The procedures of Examples 1 and 2 are repeated varying the amount of dye in the bath. The dye Red 1 is used. Color-reflectance curves of the dyed pieces are taken on the recording spectrophotometer and numerical values for the strengths of the dyeings are determined therefrom. Illustrative results are found as follows:

Strength of Shade of Dyed Fabrics Strength of Dyeing N W N W It will be observed that in the weaker dyeings and owf.) our novel process increases the strength of thedyed wool nearly fourfold, due to a greater strike of the dye for the wool. Furthermore, the skittery effect is eliminated and the dyeings are commercially satisfactory.

Example 12 The dyeing composition and procedure of Example 2 are used for the control except that the dye Red 1 is substituted for Scarlet 1. The effects of varying the components of the novel leveling composition are measured. Illustrative results aretabulated below. In each case, the dyeing with the agent on both nylon and wool is given the value of 100% for comparison.

These results illustrate the following facts.

(1) The presence of tannic acid in the composition of Example 2 causes an increase in the strike on wool of Red 1 by about 40%.

(2) The presence of the chlorinated triphenylm'ethane in the composition of Example 2 appears to have no effect on the strike of Red 1 on the wool.

' (3) Both ingredients, tannic acid and the chlorinated triphenylmethane appear to reduce the strike of Red 1 on nylon.

(4) The colloidized cationic, nonionic or anionic surfactants have very little effect on the ultimate strike of the dye foreither the nylon or the wool. However, the heathery, or skittery effect, of the dyed material is eliminated and the shade is solid.

The substitution of quebracho, gallic acid or zirconium sulfate for the tannic acid causes generally similar results to be obtained. However, the brilliance of the dyeings depends to a large extent on the solubility of these ingredients. Zirconium sulfate caused the brightest dyeings to be obtained, as will be noted more fully below.

Example 13 The procedure of Example 2 is repeated using 0.25% (owf.) of the dye Red '1. 0.025% (owf.) of a brightener white (4-methyl-7-diethylamino coumarin) is alsoadded to the dye bath at the beginning of the dyeing. Numerical components may result.

1 2 data obtained from reflectance curves of dyed fabrics show the presence of the brightener dye improves the color value of the dyeing on the nylon about 12% when compared with a similar dyeing without the brightener.

Example 14 The procedure of Example 2 is repeated using the dye Red 1 but varying the amount of tannic acid. L Illustrative results follow:

Strength of Dyeing (Percent) Percent (owl) of Tannic acid Nylon Wool 1 Used as a standard (100%).

It will be observed that the strike of the dye for the wool increases gradually as the amount of tannic acid is Example 15 In the following example, neutral-dyeing premetalized dyes of the following type formula are used:

wherein A is an unmetalized dye, such as Red 1; B also is an unmetalized dye, such as OrangeZ; and M may be chromium or cobalt. Upon metallization in aqueous solution to give a 2 to 1 complex (i.e., 2 moles dye to one atom metal) mixtures containing the above Dyes of the type A-M-B are described in US. Pat. No. 2,775,581.

Such a premetalized dye is then applied to wool-polyamide unions using the process of Example 2. Excellent, level, non-skittery shades result that are commercially satisfactory.

Example 16 For those manufacturers who desire to color woolpolyamide union yarns or fabrics in the brighter shades desirable for womens Wear, theanionic agent may be omitted and a zirconium salt, such as zirconium sulfate used instead of tannic acid, gallic acid or quebracho. For the many dy'ers who prefer to simplify their dyeing process, the various ingredients of our novel composition are premixed and only one addition is necessary. A typical equalizing composition is as follows:

A sufiicient amount of uniformly mixed composition is dissolved in water to form a one-percent solution and used in preparing a dyebath as follows:

250 ml. water 50 mg. dye, Red 1 10 ml. of the one-percent position solution of the'above com- 1.4 mg. acetic acid to give apH of about 5.5

Two 2.5-gram pieces of wool fabric and spun-nylon chaille are then entered into the dye bath at room temperature. The bath is slowly heated to the boil in about one-half hour, the pieces being turned intermittently to insure level dyeing. Dyeing and turning is continued at the boil for about one hour. The pH of the bath decreases from about 5.5 to about 4.5 at the end of the deying. Dyed pieces are then removed, rinsed and dried.

Control dyeings of the same dye on the same fabric are then made by the procedure of Example -1. Reflectance curves of the dyed pieces are then determined by the recording spectrophotometer. Illustrative curves are shown in FIGURE 7. The color values of the dyed pieces as determined from these reflectance curves follow:

These results show that the strike of the dye Red 1 for the wool has more than doubled in the presence of the equalizing composition. Further, the dyed pieces are bright and level; show no skittery effect and are commercially acceptable. t

Generally similar results are obtained when equivalent amounts of ammonium chloride, ammonium acetate or ammonium sulfate are used in place of the acetic acid. Care should be exercised that the initial pH is not lower than 5.5, preferably 6.0 after the union material is added. The final pH should beabout 4.5-5.0.

The 10 ml. of the above 1%-solution contains 100 mg. of the novel composition. This is about two percent on the weight of a S-gram piece (or pieces) of fabric. Amounts of the novel composition varying from about 1 to (5 ml. to 25 ml. of the 1%-solution, respectively) cause excellent results to be obtained. However, for economical reasons, the percentage used is maintained at the minimum necessary to produce cormnercially-acceptable dyed unions.

Example 17 strength of these dyeings, as determined from the curves.

follow:

N: 100% (standard) W=25% W=56% N=66% These results show that the presence of the urea in the nonionic surfactant has not appreciably affected the improved strike of the dye for the wool. The resultant dyeings are level, bright, and commercially acceptable.

Example 18 In repeating the procedure of Example 16, the nonionic agent (polyoxyethylene ether alcohol) is omitted from the composition, the latter being formulated as follows:

33 parts colloidized cationic agent of (U.S. Pat. No.

46 parts of pentachloro-dihydroxy-triphenylmethane sodium sulfonate 17 parts zirconium sulfate Dyeings are made as in Example 16 and compared with the control dyeings. Spectrophotometric curves of the reflectan ces of these dyeings are shown in FI GURE 9. Therefrom the following numerical values are obtained.

Example 19 In repeating the procedure of Example 16, the nonionic agent and the zirconium salt are' used in equal amounts in the following composition: t

28.50 parts colloidized cationic agent 43.00 parts pentachloro-dihydroxy-triphenylmethane sodium sulfonate 14.25 parts zirconium sulfate 14.25 parts nonionic agent (Renex 35 Dyeings are made as in Example 16. Spectrophotometric curves of the reflectances of the dyed fabrics are shown in FIGURE 10. Numerical data obtained fromthese curves follow:

N=% (standard) W=24% W=65% N"=67 The color values of the pieces dyed in the presence of the zirconium salt (W and N) are practically equal, the shades are level and bright and the dyed pieces are commercially satisfactory. Repeating the same procedure but substituting the dye Blue 1 for Red 1 generally similar results are obtained.

We claim: 1

1. A dye bath additive composition for leveling the strike of a neutral-dyeing premetalized dye in coloring union yarns and fabrics, said unions consisting of nitrogenous and polyamide materials, said additive comprising a colloidized mixture of hydrophilic colloid and cationic surfactant, a nonionic surfactant, a soluble chlorinated triphenylmethane and at least one member of the group tannic acid, gallic acid, quebracho and a zirconium salt.

2. A composition according to claim 1 in which the cationic surfactant is a condensation product of octadecyl guanidine bicarbonate and ethylene oxide.

3. A composition according to Claim 1 in which the nonionic surfactant is at least one member of the group (a) alkyl aryl alcohol, (12) polyoxyethylene ether alcohol, and (c) polyoxyethylene ether alcohol complexed with urea.

4. A composition according to claim 1 in which the soluble chlorinated triphenylmethane is pentachlorodihydroxy-triphenylmethane sodium sulfonate.

5. A composition according to claim 1 in which an anionic agent is added.

6. A composition according to claim 1 in which the nonionic surfactant is a member of the group consisting of (a) alkyl aryl alcohols, (b) polyoxyethylene ether alcohols, and (c) polyoxyethylene ether alcohols complexed with urea; the soluble chlorinated triphenylmethane is pentachloro-dihydroxy-triphenylmethane sodium sulfonate and the zirconium salt is zirconium sulfate.

7. In the process of coloring unions of nitrogenous and polyamide materials capable of producing substantially similar shades on each component of the union the steps comprising (1) prewetting the union-material in an aqueous bath comprising on the weight of the material to be colored (a) 0.5-5.0 weight percent of a colloidized mixture of hydrophilic colloid and cationic surfactant (b) 025-25 weight percent of a nonionic surfaetant (c) 1.5-5.0 weight percent of a water-soluble chlorinated triphenylmethane, and (d) 1.5-5.0 Weight percent of at least one member of the group tannic acid, gallic acid, quebracho and a zirconium salt;

(2) adding to the aqueous bath from about 0.25-3.0 weight percent of a neutral-dyeing premetalized dye;

(3) adjusting the pH of the aqueous bath from about 4.5 to 6.5 at ambient room temperature;

(4) heating the aqueous bath containing the union material to about 195 to- 215 F. to transfer the neutral-dyeing premetallized dye to the union material;

(5) separating the colored material from the aqueous bath, and

(6) thereafter rinsing and drying the colored material.

8. The process of claim 7 in which 0.25-2.5 Weight percent of an anionic surfactant is added to the aqueous bath.

' 9. The nitrogenous-polyamide product dyed by the process of claim 7.

10. An aqueous dye bath composition capable of leveldyeing nitrogenous-polyamide unions comprising about 0.25-3.0 weight percent of a neutral-dyeing premetallized dye, and about 1-4 weight percent of the composition of claim 1, weight percentages being based on the weight of the material being dyed, said aqueous dye bath at the beginning of the dyeing operation having a pH at ambient room temperatures from about 4.5 to 6.5.

References Cited by the Examiner UNITED STATES PATENTS 1,372,038 3/21 Phair -1. 8-82 1,444,786 2/23 Fleischer 8-21 5 1,672,454 6/28 Goedecke 8-82 1,812,555 6/31 Roberts 8-21 2,179,371 11/39 Dyer 8-54 2,325,972 8/43 Nusslein et al 821 2,480,775 8/49 Ryan. 10 2,520,106 8/50 Royer.

2,922,690 1/ 60 'Mueller. 2,952,506 9/60 Dellis.

2,999,731 9/61 Harding 8-21 15 FOREIGN PATENTS 759,595 10/ 5 6 Great Britain.

' OTHER REFERENCES 20 American Dyestutf Reporter, June 26, 1961, pp. 46-51.

Dyes and Chemical Technical Bulletin, vol. 15, No. 3', September 1959, pp. 116-126, pub. by E. 1. du Pont de Nemours, Wilmington, Del.

Gift: Man Made Textiles, March 1963, p. 59.

Lister: J. Soc. Dyers & Col., vol. 74, pp. 158-163.

Moncrieff: Mothproofing, pp. 59-69, pub. 1950, by Leonard Hill Ltd, London, England. v A Review of Textiles Progress, 1957, vol. 9, pp. 308-309, pub. by the Textile Institute.

3Q NORMAN G. TORCHIN, Primary Examiner.

MORRIS O. WOLK, Examiner. 

1. A DYE BATH ADDITIVE COMPOSITION FOR LEVELING THE STRIKE OF A NEUTRAL-DYEING PREMETALIZED DYE IN COLORING UNION YARNS AND FABRICS, SAID UNIONS CONSISTING OF NITROGENOUS AND POLYAMIDE MATERIALS, SAID ADDITIVE COMPRISING A COLLOIDIZED MIXTURE OF HYDROPHILIC COLLOID AND CATIONIC SURFACTANT, A NONIONIC SURFACTANT, A SOLUBLE CHLORINATED TRIPHENYLMETHANE AND AT LEAST ONE MEMBER OF THE GROUP TANNIC ACID, GALLIC ACID QUEBRACHO AND ZIRCONIUM SALT. 